Competitive Strain Modulation of Oxygen Reduction Reaction in Monolayer Binary Alloy Surfaces

Binary alloys of transition metals show great promise as catalyst materials for the cathodic oxygen-reduction reaction (ORR) in polymer-electrolyte-membrane fuel cells. However, their catalytic application is limited by a lack of understanding of the factors influencing the ORR performance. To improve this understanding, we examine the activity of monolayer AuxPt1-x surface alloys supported on Pt(111) using density functional theory. We found that the catalytic activity of AuxPt1-x/Pt(111) alloys varies significantly with the surface atomic arrangements, where phase-segregated surfaces show higher activity than those with random atomic arrangements. A key factor is a competitive strain influencing the Pt adsorption site activity. Distant Au atoms induce a long-range compressive strain that enhances Pt site activity, while adjacent Au atoms generate tensile strain that slightly reduces the Pt site activity. These findings suggest that surface alloys of elements with dissimilar lattice constants can generate competitive strain effects that modulate the activity of different adsorption sites. Our findings underscore the importance of understanding and controlling atomic arrangements in alloys to ensure good catalytic performance.